US5455371A - Method of producing difluoromethyl ethers and esters and ethers and esters produced thereby - Google Patents

Method of producing difluoromethyl ethers and esters and ethers and esters produced thereby Download PDF

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Publication number
US5455371A
US5455371A US08/076,898 US7689893A US5455371A US 5455371 A US5455371 A US 5455371A US 7689893 A US7689893 A US 7689893A US 5455371 A US5455371 A US 5455371A
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group
process according
compound
halogen
substituted
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Dieter Naumann
Wieland Tyrra
Regina Moeckel
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Solvay Fluor GmbH
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Solvay Fluor und Derivate GmbH
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C67/00—Preparation of carboxylic acid esters
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C43/00—Ethers; Compounds having groups, groups or groups
    • C07C43/02—Ethers
    • C07C43/03—Ethers having all ether-oxygen atoms bound to acyclic carbon atoms
    • C07C43/04—Saturated ethers
    • C07C43/12—Saturated ethers containing halogen
    • C07C43/123—Saturated ethers containing halogen both carbon chains are substituted by halogen atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C43/00—Ethers; Compounds having groups, groups or groups
    • C07C43/02—Ethers
    • C07C43/03—Ethers having all ether-oxygen atoms bound to acyclic carbon atoms
    • C07C43/04—Saturated ethers
    • C07C43/12—Saturated ethers containing halogen
    • C07C43/126—Saturated ethers containing halogen having more than one ether bond
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C43/00—Ethers; Compounds having groups, groups or groups
    • C07C43/02—Ethers
    • C07C43/20—Ethers having an ether-oxygen atom bound to a carbon atom of a six-membered aromatic ring
    • C07C43/225—Ethers having an ether-oxygen atom bound to a carbon atom of a six-membered aromatic ring containing halogen

Definitions

  • This invention relates to a process for producing ether and ester compounds which have a difluoromethyl group, and also to novel ether compounds containing a difluoromethyl group which are obtainable according to the process of the invention.
  • Ether and ester compounds which have a difluoromethyl group can be used in combination with surface-active compounds, e.g. phosphoric acid esters, for removing water from surfaces of objects. In combination with agents which have a lubricating effect, they can be used as lubricants.
  • difluoromethyl ethers e.g. CHF 2 OC 6 H 5 , CHF 2 OCH 2 CF 3 , CH 3 CH 2 OCF 2 H or CH 3 OCF 2 H, can be used as substitutes for fluorochlorohydrocarbons.
  • Difluoromethyl esters are intermediate products and can be used as solvents.
  • difluoromethyl ethers e.g. from enfluorane or isofluorane
  • difluoromethyl ethers takes place by reacting the unstable starting compound fluorosulphonyl difluoroacetate and alcohols, see Chen and Wu., J. Fluorine Chem. 44 (1989), pages 433 to 440.
  • R represents R 1 , R 1 C(O), or (R 1 --R 2 --X);
  • R 1 represents linear or branched alkyl with 1 to 20 carbon atoms; linear or branched alkyl with 1 to 20 carbon atoms substituted by alkoxy, substituted alkoxy, halogen, CN or NO 2 ; aryl; or aryl substituted by halogen, CN, NO 2 , C1 to C6 alkyl, aryl or aryl substituted by at least one aryl or C1 to C6 alkyl group which in turn may be substituted by one or more substituents selected from the group consisting of halogen, CN and NO 2 ; or
  • R 1 and R 2 together form an alkylene chain with 2 to 20 carbon atoms, or an alkylene chain with 2 to 20 carbon atoms substituted by halogen, CN, NO 2 , C1 to C6 alkyl or aryl, wherein said aryl and C1 to C6 alkyl substituents in turn may be substituted with one or more substituents selected from the group consisting of halogen, CN and NO 2 , and
  • R 1 has the meaning given above
  • R 2 is hydrogen; alkyl with 1 to 20 carbon atoms; or alkyl with 1 to 20 carbon atoms substituted by alkoxy, substituted alkoxy, halogen, CN, or NO 2 ; or
  • R 1 and R 2 together form an alkylene chain as defined above;
  • R 2 is hydrogen
  • R 1 has the above meaning
  • a Lewis acid with a CF 3 group-containing cadmium zinc or bismuth compound selected from the group consisting of Cd(CF 3 ) 2 , Zn(CF 3 ) 2 , Bi(CF 3 ) 3 , CdHal(CF 3 ), ZnHal(CF 3 ), BiHal(CF 3 ) 2 and BiHal 2 (CF 3 ), wherein Hal is halide, which is dissolved in an organic solvent, and hydrolyzing the resulting reaction product.
  • the objects are achieved by providing a compound corresponding to the formula
  • n 2, 3 or 4
  • Y represents an alkyl group containing 1 to 4 carbon atoms, or to the formula
  • R stands for R 1 , (R 1 --R 2 --X) or for R 1 C(O) and R 1 is linear or branched alkyl with 1 to 20 carbon atoms; linear or branched alkyl with 1 to 20 carbon atoms substituted by alkoxy, substituted alkoxy, halogen, CN, NO 2 ; aryl; aryl substituted by halogen, CN, NO 2 , C1 to C6 alkyl, aryl, or aryl substituted by one or more aryl or C1 to C6 alkyl groups, these aryl or C1 to C6 alkyl groups themselves being substituted by one or more substituents selected from the group consisting of halogen, CN and NO 2 ; or
  • R 1 and R 2 together form an alkylene chain with 2 to 20 carbon atoms; an alkylene chain with 2 to 20 carbon atoms substituted by halogen, CN, NO 2 , C1 to C6 alkyl, aryl; or an alkylene chain with 2 to 20 carbon atoms substituted by aryl or C1 to C6 alkyl, these aryl or C1 to Cy alkyl groups themselves being substituted by one or more substituents selected from the group consisting of halogen, CN and NO 2 , and
  • X is halogen, in particular chloride or fluoride
  • R 1 has the meaning defined above
  • R 2 is hydrogen, alkyl with 1 to 20 carbon atoms, alkyl with 1 to 20 carbon atoms optionally substituted by alkoxy, substituted alkoxy, halogen, CN, NO 2 , or
  • R 1 and R 2 together form an alkylene chain as defined above;
  • R 2 is hydrogen and R 1 has the above meaning, are reacted in the presence of a Lewis acid with a cadmium, zinc or bismuth compound containing the CF 3 group and selected from the group consisting of Cd(CF 3 ) 2 , Zn(CF 3 ) 2 , Bi(CF 3 ) 3 , CdHal(CF 3 ), ZnHal(CF 3 ), BiHal(CF 3 ) 2 and BiHal 2 (CF 3 ), wherein Hal is halide, preferably bromide or chloride, which is dissolved in a complexing, aprotic organic solvent, and the resulting reaction product is hydrolyzed.
  • a Lewis acid with a cadmium, zinc or bismuth compound containing the CF 3 group and selected from the group consisting of Cd(CF 3 ) 2 , Zn(CF 3 ) 2 , Bi(CF 3 ) 3 , CdHal(CF 3 ), ZnHal(CF 3 ), BiHal(CF 3
  • alkoxy may, for example, denote C1 to C4 alkoxy.
  • substituted alkoxy may, for example, denote C1 to C4 alkoxy subsitituted by one or more halogen atoms, particularly by fluorine atoms.
  • the R 2 group is cleaved off.
  • R 2 is preferably C1-C5-alkyl, in particular methyl, ethyl or t-butyl.
  • R 1 is preferably C1-C6-alkyl or phenyl, or C1-C6-alkyl or phenyl substituted by halogen, in particular one or more chlorine and/or fluorine atoms.
  • R 1 may be methyl, ethyl, phenyl, fluoromethyl, difluorochloromethyl, trifluoromethyl. 2,2,2-trifluoroethyl, pentafluorophenyl.
  • R 1 in the compounds of the general formula (I) stands for C1-C2-alkylene substituted by C1-C2-alkoxy, or for A-O-B-O-C, wherein A and B stand for C1-C2-alkylene and C stands for C1-C4-alkyl.
  • R 1 and R 2 form an alkylene chain with 2 to 4 carbon atoms or an alkylene chain with 2 to 4 carbon atoms substituted by one or more halogen atoms, in particular chlorine and/or fluorine.
  • Lewis acids can be used. Suitable examples include halogen compounds of elements of groups III and IV of the periodic table. Halogen compounds of elements of group III, e.g. boron, aluminium, indium and gallium, in particular chlorides or fluorides, are especially suitable. Halogen compounds of boron and indium are very especially suitable. Boron trichloride, indium trichloride, boron trifluoride and adducts of boron trifluoride, in particular with nitriles, such as acetonitrile, ethers such as dimethyl ether, diethyl ether, methyl-t-butyl ether, are very highly suitable. Boric acid esters are also suitable.
  • the zinc, bismuth or cadmium compound is used dissolved in an organic solvent. It is present in the solvent in the form of an adduct.
  • Hal may also stand for iodide.
  • cadmium compounds of the general formula (CF 3 ) 2 Cd.D may be dissolved in a corresponding solution.
  • the cadmium compound is already present as an adduct.
  • Compounds of this type are known, cf. H. Lange, D. Naumann, J. Fluor. Chem., 26 (1984), pages 1 to 18.
  • the symbol "D" represents 2 molecules of those Lewis bases which can only provide one pair of electrons for coordination, or 1 molecule of those Lewis bases which can provide two or more pairs of electrons for coordination.
  • glyme ethylene glycol dimethyl ether
  • diglyme diethylene glycol dimethyl ether
  • TMED N,N,N',N'-tetramethyl ethylene diamine
  • this solution of the trifluoromethyl compound can be produced by producing the trifluoromethyl cadmium compound in a solution which contains complexing solvent, and using it in situ in the process according to the invention, as described in the literature source quoted.
  • the complexing solvent stabilizes the trifluoromethyl cadmium compound. It is advantageous if during the reaction there is always a quantity of complexing solvent which is sufficient for stabilization in the reaction mixture. However, it is also clear to a person skilled in the art that the solvent need not consist of this complexing solvent.
  • non-complexing, inert organic solvents which are miscible with the complexing solvent may also be present in the reaction mixture. These include, for example, halogenated hydrocarbons such as chloroform, hydrocarbons such as pentane, hexane or petroleum ether fractions, or aromatic solvents such as toluene.
  • the content of such non-complexing solvents in the solvent mixture may be up to 100% by weight, for example between 0 and 90% by weight.
  • Aprotic, polar organic Lewis base compounds which may provide 1, 2 or more pairs of electrons for coordinate bonding are used as complexing solvents.
  • these include aliphatic ethers, e.g. dialkyl ethers such as diethyl ether, cycloaliphatic ethers, for example tetrahydrofuran, oligomeric aliphatic ethers, for example the "glyme” and “diglyme” mentioned above, nitriles, for example acetonitrile, oligomeric tetraalkyl-substituted diamines or polyamines, for example tetramethyl ethylene diamine, mixed aliphatic-aromatic ethers (e.g. anisole), lactams, formamides, carboxylic acid amides, and sulfones.
  • aliphatic ethers e.g. dialkyl ethers such as diethyl ether, cycloaliphatic ethers, for example t
  • ether compounds as solvents, it is advantageous to use as the solvent, the ether starting compound of Formula (II) which is also used as a reactant.
  • Zn(CF 3 ) 2 .2D The production of Zn(CF 3 ) 2 .2D is described by H. Lange and D. Naumann in J. Fluorine Chem. 26 (1984), pages 435 and 444. According to this article, CF 3 I is reacted with dialkyl zinc compounds, e.g. dimethyl zinc or diethyl zinc, in the presence of a Lewis base, e.g. glyme or diglyme, pyridine, forming Zn(CF 3 ) 2 .2D.
  • dialkyl zinc compounds e.g. dimethyl zinc or diethyl zinc
  • the reaction of the zinc, bismuth or cadmium compound with the respective starting compound used takes place at a temperature of -78° C. to +20° C.
  • the molar ratio of the starting compound (II) to the trifluoromethyl cadmium compound used may be in the range of about 1:1 to 20:1. It is preferably between about 2:1 and 4:1.
  • the use of (II) as a solvent is advantageous.
  • the process is carried out by initially producing a mixture of the trifluoromethyl metal compound and the starting compound in the organic solvent and then adding the Lewis acid.
  • the molar ratio of metal compound to Lewis acid is between about 1:1.5 and 1:5. Preferably it lies between about 1:1.5 and 1:3.
  • the Lewis acid for example a boron trihalide adduct or indium halide such as indium trichloride, may be added as a solid. It is of course also possible to add a slurry or solution of the Lewis acid, for example in the solvent used.
  • an exothermic reaction then begins.
  • an inert gas such as nitrogen may be passed over the reaction mixture.
  • the reaction mixture also may be left for some time, for example up to several hours, in order to complete the reaction.
  • a molar quantity of a protic compound for example an acid, an alcohol or, advantageously, water, is added to the reaction mixture.
  • volatile constituents may be separated by fractional distillation. In this manner, the desired difluoromethyl ether compound of formula (I) can be isolated.
  • the process of the invention is suitable for producing compounds of the general formula (I) in which R has the meaning given above.
  • the process of the invention is particularly suitable for producing compounds of formula (I) in which R is CH 3 , C 2 H 5 , CH 2 CF 3 , (CH 2 ) 3 CH 3 , (CH 2 ) 4 Cl, C 6 H 5 , C 6 F 5 or CH 2 CH 2 --O--CH 2 CH 2 --OCH 3 .
  • the compounds obtainable according to the process of the invention can be used for the purposes mentioned a the beginning of this specification for which they are usually used, e.g. as intermediate products in chemical synthesis, as lubricants, coolants etc.
  • This compound was produced from trifluoromethyl iodide, diglyme and dimethyl cadmium in accordance with the method in H. Lange, D. Naumann, J. Fluor. Chem. 26 (1984), page 13.
  • the second fraction (0° C. to RT) contained only traces of difluoromethyl-2,2,2-trifluoroethyl ether, while presumably CF 3 CH 2 OCH 2 CF 3 was present as the main product (integration ratio: 1:15).

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US08/076,898 1992-06-17 1993-06-15 Method of producing difluoromethyl ethers and esters and ethers and esters produced thereby Expired - Fee Related US5455371A (en)

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DE4219811A DE4219811A1 (de) 1992-06-17 1992-06-17 Herstellung von Difluormethylethern und -estern
DE4219811.9 1992-06-17

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EP (1) EP0574839B1 (de)
JP (1) JPH0672937A (de)
AT (1) ATE143933T1 (de)
DE (2) DE4219811A1 (de)

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JP4976038B2 (ja) 2006-03-29 2012-07-18 シスメックス株式会社 血液学的試料の測定方法
JP6249472B2 (ja) * 2013-08-30 2017-12-20 国立大学法人東京工業大学 ビス（トリフルオロメチル）亜鉛・ｄｍｐｕ錯体、その製造方法並びにそれを用いたトリフルオロメチル基含有化合物の製造方法
DE102016001494A1 (de) * 2015-09-23 2017-03-23 Merck Patent Gmbh Bismutverbindungen enthaltend Perfluoralkylgruppen als Lewis-Säure Katalysatoren

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0352034A2 (de) * 1988-07-18 1990-01-24 Boc, Inc. Verfahren und Zwischenverbindung zur Herstellung von CHF2OCHFCF3
US4922041A (en) * 1987-05-22 1990-05-01 Kali-Chemie Ag Method for producing CF3 I
EP0388114A2 (de) * 1989-03-14 1990-09-19 BOC Health Care, Inc. Verfahren zur Herstellung von 1,2,2,2-Tetrafluorethyl-Difluormethyläther

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4922041A (en) * 1987-05-22 1990-05-01 Kali-Chemie Ag Method for producing CF3 I
EP0352034A2 (de) * 1988-07-18 1990-01-24 Boc, Inc. Verfahren und Zwischenverbindung zur Herstellung von CHF2OCHFCF3
EP0388114A2 (de) * 1989-03-14 1990-09-19 BOC Health Care, Inc. Verfahren zur Herstellung von 1,2,2,2-Tetrafluorethyl-Difluormethyläther

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Title
Bagnall et al. J. Fluorine Chem. 13:123 40 (1979). *
Bagnall et al. J. Fluorine Chem. 13:123-40 (1979).
Boit, Beilsteins Handbuch der organischen Chemie, vol. 6/2 , p. 611 (1978). *
Boit, Beilsteins Handbuch der organischen Chemie, vol. 6/2', p. 611 (1978).
Chemical Abstracts, 103:(19) 160622c (1985). *
Chemical Abstracts, 110:(13) 114999c (1985). *
Chen et al., J. Fluorine Chem., 44:433 40 (1989). *
Chen et al., J. Fluorine Chem., 44:433-40 (1989).
Chen et al., J. Org. Chem. 54:3023 27 (1989). *
Chen et al., J. Org. Chem. 54:3023-27 (1989).
Hine et al., J. Am. Chem. Soc. 79:5493 96 (1957). *
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Lange et al., J. Fluorine Chem., 26:1 18 (1984). *
Lange et al., J. Fluorine Chem., 26:1-18 (1984).
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Mitsch et al., J. Heterocyclic Chem. 2:152 56 (1965). *
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Naumann et al., J. Organomet. Chem. 334:323-28 (1987).

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EP0574839A2 (de) 1993-12-22
DE4219811A1 (de) 1993-12-23
DE59304082D1 (de) 1996-11-14
ATE143933T1 (de) 1996-10-15
US5639921A (en) 1997-06-17
EP0574839A3 (en) 1994-06-01
EP0574839B1 (de) 1996-10-09
JPH0672937A (ja) 1994-03-15

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